WO2009127366A1 - Polycarbonates having rearrangement structures, cyclic and linear oligomers and also improved flow behaviour - Google Patents
Polycarbonates having rearrangement structures, cyclic and linear oligomers and also improved flow behaviour Download PDFInfo
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- WO2009127366A1 WO2009127366A1 PCT/EP2009/002662 EP2009002662W WO2009127366A1 WO 2009127366 A1 WO2009127366 A1 WO 2009127366A1 EP 2009002662 W EP2009002662 W EP 2009002662W WO 2009127366 A1 WO2009127366 A1 WO 2009127366A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
Definitions
- This invention relates to compositions having improved rheological properties based on polycarbonate with rearrangement structures and cyclic and linear OH gomers, as well as shaped articles and extrudates of these polycarbonate compositions.
- EP-A 0 517 044, WO 2006/072344 and EP-A 1 609 818 and documents cited therein describe, for example, the phase boundary surfaces and the melt process for the production of polycarbonate.
- EP-A 0953605 describes the use of cyclic aromatic carbonates as flow improvers and agents for improving the mold transferability of linear aromatic polycarbonates.
- phenyl rings independently of one another may be monosubstituted or disubstituted by C 1 -C -alkyl, halogen, such as chlorine or bromine, preferably C 1 -C 4 -alkyl, especially methyl, and X has the meaning given for formula (Ia),
- the amount of the structural units (I) to (IV) in total is generally from 50 to 900 ppm, based on the underlying polycarbonate, furthermore comprising in total linear and cyclic oligomers in an amount of from 0.1 to 2% by weight. % based on the total composition, the
- linear oligomers are those of the formulas (V) to (DC)
- n 1-6 wherein the amount of structures (VIII) and (IX) is less than 0.001% by weight, and the cyclic oligomers are those of the general formula (X) where n is an integer from 2 to 6 and
- Z is a radical of the formula (Ia)
- R 1 and R 2 independently of one another are H, C 1 -C 8 -alkyl, preferably H or C 1 -C 4 -alkyl, particularly preferably hydrogen or methyl, and
- X is a single bond, Cj- to C ⁇ -alkylene, C 2 - to Cs-alkylidene or C 5 - to Ce- Cycloalkyli- den, which may be substituted by C r to C 6 -alkyl, preferably methyl or ethyl, is.
- the structural units of the formulas (I) to (FV) are also referred to simply as rearrangement structures.
- the structural units are derived and result from the diphenols or diphenol mixtures used for the preparation of the polycarbonate.
- the phenyl rings of the rearrangement structures unsubstituted.
- the cyclic oligomers of the general formula (X) present in the polycarbonate compositions according to the invention are preferably used in amounts of 0.2 to 1.2, more preferably 0.2 to 1.1 and most preferably 0.3 to 1 part by weight. % contain.
- linear oligomers of the general formula (V) to (VII) which are contained in the polycarbonate compositions according to the invention are preferably in amounts of from 0.2 to 1.2, particularly preferably from 0.3 to 1.1 and very particularly preferably from 0.4 to 0, 9 wt .-% included.
- the rearrangement structures defined above occur in different amounts and proportions to one another. Their amount can be determined by total saponification of the polycarbonate composition.
- the low-molecular degradation products of the formulas (Ia) to (FVa) which are characteristic of the respective rearrangement structure and whose amount is determined by means of HPLC are formed.
- the amount of the compound of the formula (Ia) released thereby is 50 to 800 ppm, preferably from 70 to 700 ppm, more preferably from 100 to 600 ppm and most preferably from 100 to 550 ppm.
- the amount of the compound of formula (Ha) released thereby is 0 (below the detection limit of ⁇ 5 ppm) to 100 ppm, preferably from 0 to 90 ppm, more preferably from 0 to 80 ppm and most preferably from 0 to 70 ppm.
- the amount of compound of formula (IIIa) released thereby is 0 (below the detection limit of ⁇ 5 ppm) to 60 ppm, preferably from 0 to 50 ppm, more preferably from 5 to 40 ppm, and most preferably from 5 to 30 ppm.
- the amount of compound of formula (IVa) released thereby is 0 (below the detection limit of ⁇ 5 ppm) to 300 ppm, preferably from 5 to 280 ppm, more preferably from 5 to 270 ppm and most preferably from 10 to 260 ppm.
- the amount of the structures of the formula (I) to (IV) is set equal to the amount of the released compounds of the formulas (Ia) to (IVa).
- the polycarbonates have the following nonuniformity, the nonuniformity for different molecular weight ranges being as follows: for low-viscosity PC according to the invention having an average molecular weight (weight average) of from 18,000 to 22,000 g / mol, U is from 1.08 to 1.18, preferably from 1.10 to 1.16,
- U is 1.18 to 1.60, preferably 1.20 to 1.55, particularly preferably 1.20 to 1.50, very particularly preferably 1.20 to 1.45,
- U is 1.25 to 1.65, preferably 1.25 to 1.60, particularly preferably 1.25 to 1.50 and very particularly preferably from 1.30 to 1.45,
- U is 1.50 to 1.95, preferably 1.55 to 1.90, particularly preferably 1.55 to 1 , 85, most preferably 1.55 to 1.80.
- compositions of the invention which contain the relocation essential structures and reduced content of oligomers (cyclic and linear), and preferably a narrower molecular weight distribution (minor nonuniformity U), are aromatic dihydroxy compounds, with carbonic acid diesters with the aid of certain catalysts and optionally further Additives in the melt transesterified.
- polycarbonate compositions according to the invention having reduced cyclic carbonate contents and rearrangement structures as well as a narrower molecular weight distribution (smaller nonuniformity U) are prepared by the melt transesterification process from aromatic dihydroxy compounds, with carbonic acid diesters in the presence of ammonium or phosphonium salts as catalysts.
- suitable diphenols are those of the formula (1)
- R 1 and R 2 are each independently H, Q-Cg-alkyl, preferably H or C] - C 4 -alkyl, particularly preferably hydrogen or methyl, and
- X represents a single bond, Q to C 6 alkylene, C 2 - to C 5 alkylidene or C 5 - to C 6 - to Cycloalkyli- which may be substituted with Q -C ö alkyl, preferably methyl or ethyl , stands.
- X is preferably a single bond, methylene, isopropylidene, cyclohexylidene or 3,3,5-trimethylcyclohexylidene, particularly preferably isopropylidene or 3,3,5-trimethylcyclohexylidene.
- dihydroxyaryl compounds examples include dihydroxybenzenes, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, and their nuclear alkylated compounds.
- Dihydroxyaryl compounds are well known or can be prepared by well-known methods (e.g., WO 2006/072344, EP-A 1609818 and references cited therein).
- Preferred diphenols of the formula (1) are: 2,2-bis (4-hydroxyphenyl) propane (BPA), bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 4,4'-dihydroxydiphenyl ,
- Both a dihydroxyaryl compound to form homopolycarbonates and various dihydroxyaryl compounds to form copolycarbonates can be used.
- the latter is particularly important if products with special property combinations are to be produced.
- the dihydroxyaryl compounds can also be used with residual contents of the monohydroxyaryl compounds from which they have been prepared or the low molecular weight oligocarbonates containing residual monohydroxyaryl compounds which have been eliminated in the preparation of the oligomers.
- the residual contents of monohydroxyaryl compounds can be up to 20%, preferably 10%, more preferably up to 5% and very particularly preferably up to 2% (see, for example, EP-A 1 240 232).
- the dihydroxyaryl compounds used, as well as all other raw materials, chemicals and auxiliaries added to the synthesis may be contaminated with the impurities derived from their own synthesis, handling and storage, although it is desirable and desirable to work with as clean as possible raw materials, chemicals and adjuvants.
- Suitable diaryl carbonates for the reaction with the dihydroxyaryl compounds are those of the formula (2)
- R, R 'and R "independently of one another can be identical or different and represent hydrogen, optionally branched CpC 34 alkyl, C 7 -C 34 - alkylaryl or C 6 -C 34 -aryl, R WEI terhin also -COO- R '", where R'" is hydrogen, optionally branched Ci- C 34 alkyl, C 7 -C 34 -alkylaryl or C 6 -C 34 -aryl.
- diaryl carbonates are described, for example, in EP-A 1 609 818.
- Preferred diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl phenyl carbonate.
- diphenyl carbonate is particularly preferred.
- the diaryl carbonates can also be used with residual contents of the monohydroxyaryl compounds from which they were prepared.
- the residual contents of the monohydroxyaryl compounds can be up to 20%, preferably 10%, more preferably up to 5% and most preferably up to 2%.
- the diaryl carbonates are generally from 1.02 to 1.30 mol, preferably from 1.04 to 1.25 mol, more preferably from 1.06 to 1.22 mol, most preferably from 1.06 to 1.20 moles per mole of dihydroxyaryl used. It is also possible to use mixtures of the abovementioned diaryl carbonates.
- R, R 1 and R “have the meaning given for R 1 and R 2 in the formula (Ia).
- Preferred is PPh-n-n-1-ol, dd .. hh .. all-radical-radical ((33)) sstteehheenn f Schoürr HH ..
- a monohydroxyaryl compound is to be selected whose boiling point is above that of the monohydroxyaryl compound which was used to prepare the diaryl carbonate used.
- the monohydroxyaryl compound can be added at any time in the course of the reaction. It is preferably added at the beginning of the reaction or else at any point in the course of the process.
- the proportion of free monohydroxyaryl compound may be 0.2-20 mol%, preferably 0.4-10 mol%, based on the dihydroxyaryl compound.
- the end groups may also be altered by the concomitant use of a diaryl carbonate whose base mono-hydroxyaryl compound has a higher boiling point than the basic monohydroxyaryl compound of the predominantly used diaryl carbonate.
- the diaryl carbonate can be added at any time in the course of the reaction. It is preferably added at the beginning of the reaction or else at any point in the process.
- the proportion of the diaryl carbonate with the higher-boiling base monohydroxyaryl compound in the total amount of diaryl carbonate used can be 1 to 40 mol%, preferably 1 to 20 mol% and particularly preferably 1 to 10 mol%.
- the catalysts used in the melt transesterification process according to the invention are ammonium or phosphonium salts, referred to below as onium salts. Preference is given to using phosphonium salts.
- Phosphonium salts in the context of the invention are those of the general formula (4)
- R 7 "10, the same or different C r Ci 0 alkyls, C 6 -C 14 -ATyIe, Cy-Cis-arylalkyls or C 5 -
- C 6 -cycloalkyls preferably methyl or C 6 -C 4 -aryls, particularly preferably methyl or phenyl
- catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide and tetraphenylphosphonium phenolate; particularly preferred is tetraphenylphosphonium phenolate.
- catalysts may be used as cocatalyst in addition to the onium salt of the above type to increase the rate of polycondensation.
- alkaline salts of alkali metals and alkaline earth metals such as hydroxides, alkoxides and aryl oxides of lithium, sodium and potassium, preferably hydroxides, alkoxides or aryl oxides of sodium.
- alkaline salts of alkali metals and alkaline earth metals such as hydroxides, alkoxides and aryl oxides of lithium, sodium and potassium, preferably hydroxides, alkoxides or aryl oxides of sodium.
- sodium hydroxide and sodium phenolate as well as the disodium salt of 2,2-bis- (4-hydroxyphenyl) -propane.
- the amounts of alkaline salts of alkali metals and alkaline earth metals as the cocatalyst may be in the range of 1 to 500 ppb, preferably 5 to 300 ppb, and most preferably 5 to 200 ppb, each calculated as sodium and based on the polycarbonate to be formed ,
- alkaline salts of alkali metals and alkaline earth metals can already be used in the preparation of the oligocarbonates, that is to say at the beginning of the synthesis, or they can also be mixed in before the polycondensation in order to suppress unwanted side reactions.
- the addition of the catalysts takes place in solution in order to avoid harmful excess concentrations during the metering.
- the solvents are system and process inherent compounds such as dihydroxyaryl compounds, diaryl carbonates or monohydroxyaryl compounds. Particular preference is given to monohydroxyaryl compounds because it is familiar to the person skilled in the art that the dihydroxyaryl compounds and diaryl carbonates readily change and decompose at already slightly elevated temperatures, in particular under the action of a catalyst.
- These include polycarbonate grades.
- the preferred compound is phenol. Phenol is also available therefore already mandatory, because the preferably used catalyst tetraphenylphosphonium phenolate is isolated in the production as a mixed crystal with phenol.
- the weight average molecular weights of the polycarbonates are generally from 15,000 to 50,000, preferably from 17,000 to 40,000, more preferably from 17,000 to 34,000 g / mol, and are determined by GPC against a polycarbonate calibration.
- the polycarbonates generally have an extremely low content of cations and anions of in each case less than 60 ppb, preferably ⁇ 40 ppb and particularly preferably ⁇ 20 ppb (calculated as Na cation), with cations of those of alkali metals and alkaline earth metals being present which may originate, for example, as an impurity from the raw materials used and the phosphonium and ammonium salts.
- Other ions such as Fe, Ni, Cr, Zn, Sn, Mo, Al ions and their homologues can be contained in the raw materials or originate from the materials of the plant used by removal or corrosion.
- the content of these ions is less than 2 ppm in total, preferably less than 1 ppm and more preferably less than 0.5 ppm.
- Anions are those of inorganic acids and of organic acids in equivalent amounts (eg, chloride, sulfate, carbonate, phosphate, phosphite, oxalate, etc.).
- the aim is thus the smallest amounts that can be achieved only by using pure raw materials.
- pure raw materials are e.g. only after cleaning procedures such as recrystallization, distillation, topping with washes u. ⁇ . Available.
- the erf ⁇ ndungshacke process for the production of polycarbonate after Umest ceremoniessverfah- ren can be designed batchwise or continuously. After the dihydroxy aryl compounds and diaryl carbonates, optionally with other compounds, are in the form of a melt, the reaction is started in the presence of the catalyst essential to the invention. The conversion or the molecular weight is increased with increasing temperatures and falling pressures in suitable apparatus and devices by removing the cleaving Monohydroxyarylverbin- fertil until the desired final state is reached.
- the loss rate of the diaryl carbonate given via the choice of the method or plant for preparing the polycarbonate via the vapors and optionally added compounds, for example a higher-boiling monohydroxyaryl compound, the end groups are characterized in type and concentration.
- the temperatures over the entire process are generally 180 to 330 0 C at pressures of 15 bar, absolute to 0.01 mbar, absolute.
- the continuous process for the preparation of polycarbonates is characterized in that one or more dihydroxyaryl compounds with the diaryl carbonate, optionally also other added reactants using the catalysts, after a precondensation without separating the Monohydroxyarylharm formed in then then following several reaction Evaporator stages at gradually increasing temperatures and gradually falling pressures, the molecular weight is built up to the desired level.
- the apparatus, apparatuses and reactors suitable for the individual reaction-evaporator stages are, according to the process course, heat exchangers, expansion apparatuses, separators, columns, evaporators, stirred vessels and reactors or other commercially available apparatuses which provide the necessary residence time at selected temperatures and pressures.
- the chosen devices must provide the necessary heat input and be designed to meet the ever-increasing melt viscosities.
- All devices are connected by pumps, piping and valves.
- the pipelines between all devices should be as short as possible and the bends of the lines should be kept as low as possible to avoid unnecessarily prolonged dwell times.
- the external that is to say technical framework conditions and concerns for installations of chemical plants have to be considered.
- the reactants can either be melted together or else the solid dihydroxyaryl compound in the diaryl carbonate melt or the solid diaryl carbonate can be dissolved in the melt of the dihydroxyaryl compound or both raw materials are melted, preferably directly from the manufacturing, merged.
- the residence times of the separate melts of the raw materials, in particular those of the melt of the dihydroxyaryl compound, are adjusted as short as possible.
- the melt mixture can stay longer at correspondingly lower temperatures without sacrificing quality.
- the catalyst preferably dissolved in phenol, admixed and the melt is heated to the reaction temperature.
- This is at the beginning of the technically significant process for the production of polycarbonate from 2,2-bis (4-hydroxyphenyl) propane and diphenyl 180 to 220 0 C, preferably 190 to 210 0 C, most preferably 190 0 C.
- the reaction equilibrium is adjusted without removing the hydroxyaryl compound formed.
- the reaction can be run at atmospheric pressure, but for technical reasons even at overpressure.
- the preferred pressure in technical systems is 2 to 15 bar absolute.
- the melt mixture is expanded in a first vacuum chamber whose pressure is set to 100 to 400 mbar, preferably to 150 to 300 mbar, and then directly heated to the inlet temperature in a suitable device at the same pressure.
- the resulting hydroxyaryl compound is evaporated with remaining monomers.
- the reaction mixture is in a second vacuum chamber, the pressure of 50 to 200 mbar, preferably 80 to 150 mbar, relaxed and directly afterwards in a suitable device at the same pressure to a temperature of 190 to 250 0 C, preferably 210 to 240 0 C, particularly preferably 210 to 230 0 C, heated.
- the resulting Hydroxyarylharm is evaporated with remaining monomers.
- the reaction mixture in a third vacuum chamber whose pressure is 30 to 150 mbar, preferably 50 to 120 mbar, relaxed and directly afterwards in a suitable device at the same pressure to a temperature of 220 to 280 0 C, preferably 240 to 270 0 C, particularly preferably 240 to 260 0 C, heated.
- the resulting HydroxyarylENS is evaporated with remaining monomers.
- the reaction mixture is in a further vacuum chamber whose pressure at 5 to 100 mbar, preferably 15 to 100 mbar, particularly preferably 20 to 80 mbar , Relaxed and directly afterwards in a suitable device at the same pressure to a temperature of 250 to 300 0 C, preferably 260 to 290 0 C, particularly preferably 260 to 280 0 C, heated.
- a suitable device at the same pressure to a temperature of 250 to 300 0 C, preferably 260 to 290 0 C, particularly preferably 260 to 280 0 C, heated.
- the resulting hydroxyaryl compound is evaporated with remaining monomers.
- the number of these stages, here exemplarily 4 can vary between 2 and 6.
- the temperatures and pressures are to be adjusted accordingly when changing the step to obtain comparable results.
- the achieved in these stages rel.
- Viscosity of the oligomeric carbonate is between 1.04 and 1.20, preferably between 1.05 and 1.15, particularly preferably between 1.06 and 1.10.
- the oligocarbonate thus produced is required after a residence time of 5 to 20 minutes in a sump original, where appropriate with pumping at the same pressure and same temperature as in the last flash / evaporator stage in a disk or basket reactor and at 250 to 310 0 C, preferred 250 to 290 0 C, more preferably 250 to 280 0 C, at pressures of 1 to 15 mbar, preferably 2 to 10 mbar, at residence times of 30 to 90 minutes, preferably 30 to 60 minutes, further condensed.
- the product reaches a rel. Viscosity of 1.12 to 1.28, preferably 1.13 to 1.26, more preferably 1.13 to 1.24.
- the melt leaving this reactor is brought to the desired final viscosity or the final molecular weight in a further disk or basket reactor.
- the temperatures betra- gen 270 to 330 0 C, preferably 280 to 320 0 C, particularly preferably 280 to 310 0 C, the pressure 0.01 to 3 mbar, preferably 0.2 to 2 mbar, with residence times of 60 to 180 min , preferably 75 to 150 min.
- the rel. Viscosities are adjusted to the level required for the intended application and are 1.18 to 1.40, preferably 1.18 to 1.36, more preferably 1.18 to 1.34.
- the function of the two basket reactors or disk reactors can also be summarized in a basket reactor or disk reactor.
- the vapors from all process stages are immediately derived, collected and processed. This work-up is usually carried out by distillation in order to achieve high purities of the recovered materials. This can be done, for example, according to German Patent Application No. 10 100 404. Recovery and isolation of the cleaved monohydroxy aryl compound in its purest form is a matter of course from an economic and ecological point of view.
- the monohydroxyaryl compound can be used directly for producing a dihydroxyaryl compound or a diaryl carbonate.
- the disk or basket reactors are characterized by the fact that they provide a very large, constantly renewing surface on a vacuum at high residence times.
- the disk or basket reactors are geometrically formed according to the melt viscosities of the products. Suitable examples are reactors, as described in DE 44 47 422 C2 and EP A 1 253 163, or two wave reactors, as described in WO A 99/28 370.
- the oligocarbonates, also very low molecular weight, and the finished polycarbonates are usually required by gear pumps, screws of various types or positive displacement pumps special design.
- Particularly suitable materials for the production of apparatus, reactors, pipelines, pumps and valves are stainless steels of the type Cr Ni (Mo) 18/10 such. B. 1.4571 or 1.
- the polycarbonate obtained may be provided with other conventional additives and additives (for example auxiliaries and reinforcing substances) after addition of the inhibitors according to the invention for the purpose of altering properties.
- additives and additives serves to prolong the service life (eg hydrolysis or degradation stabilizers), to improve color stability (eg thermal and UV stabilizers), to simplify processing (eg demulsifiers, flow aids), to improve the performance properties (eg antistatic), improving the flame retardancy, influencing the visual impression (eg organic colorants, pigments) or adapting the polymer properties to specific loads (impact modifiers, finely divided minerals, fibers, quartz powder, glass and carbon fibers).
- Such additives and additives are e.g. in "Plastics Additives", R. Gumbleter and H. Müller, Hanser Publishers 1983.
- Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168), tetrakis (2,4-di-tert-butylphenyl) [l, lbiphenyl] -4,4 r -diylbisphosphonite are preferably suitable as thermal stabilizers.
- Trisoctyl phosphate, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076), bis (2,4-dicumylphenyl) pentaerythritol diphosphite (Doverphos S-9228), bis (2,6- di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (ADK STAB PEP-36) or triphenylphosphine. They are used alone or in a mixture (eg Irganox B900 or Doverphos S-92228 with Irganox B900 or Irganox 1076).
- Pentaerythritol tetrastearate, glycerol monostearate, stearyl stearate or propanediol stearate are preferably suitable as mold release agents. They are used alone or in a mixture.
- AJs light stabilizers are preferably benzotriazoles, triazines, benzophenones, cyanoacrylates, cinnamic acid esters or oxalanilides. They are used alone or in a mixture. These additives and additives can be added to the polymer melt individually or in any desired mixtures or several different mixtures, specifically directly during the isolation of the polymer or after the melting of granules in a so-called compounding step.
- the additives and additives or mixtures thereof may be added as a solid, ie as a powder, or as a melt of the polymer melt.
- Another type of dosing is the use of masterbatches or mixtures of masterbatches of the additives or additive mixtures.
- Suitable additives are described, for example, in Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999 or Plastics Additives Handbook Hans Zweifel, Hanser, Kunststoff 2001.
- inhibitors (quenchers) for deactivating catalyst residues of the polymer melt can be dissolved in pure form, in an inert solvent or added as a masterbatch.
- Suitable inhibitors are acid components such as Lewis or Brönsted acids or esters of strong acids.
- the pKa of the inhibitor should not be greater than 5, preferably less than 3.
- the acid component or its esters are added in order to deactivate the reaction mixture, ie in the ideal case to completely bring the reaction to a standstill.
- the acid component is added in concentrations of ⁇ 20 ppm, preferably ⁇ 10 ppm, more preferably ⁇ 5 ppm and most preferably ⁇ 2.5 ppm. After reaching the desired molecular weight, the detectable P amount is in the 1 ppm range.
- the molar inhibitor amounts to be used according to the invention are below the molar residual amounts of catalyst to be assumed from the P value.
- Suitable acid components are: ortho-phosphoric acid, phosphorous acid, pyrophosphoric acid, hypophosphoric acid, polyphosphoric acids, benzenephosphonic acid, sodium dihydrogen phosphate, boric acid, arylboronic acids, hydrochloric acid (hydrogen chloride), sulfuric acid, ascorbic acid, oxalic acid, benzoic acid, salicylic acid, formic acid, Acetic acid, adipic acid, citric acid, benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid and all other phenyl-substituted benzenesulfonic acids, nitric acid, terephthalic acid, isophthalic acid, stearic acid and other fatty acids, acid chlorides such as phenyl chloroformate, stearic acid chloride, acetoxy-BP-A, benzoyl chloride and esters, Half ester and bridged ester of the
- Preferred suitable inhibitors are bridged esters of organic sulfur-containing acids selected from at least one compound
- R 1 is independently hydrogen or Ci-C2o-alkyl, preferably Q-Cg-alkyl, particularly preferably represents unsubstituted Ci-C ⁇ -alkyl, very particularly preferably Ci-C 4 -alkyl-CyI, wherein alkyl by halogen may be substituted, in particular represents hydrogen or methyl,
- R 2 and R 3 are independently hydrogen, or C] -C6 alkyl, C 4 -C 3 o-alkylcarboxyl, preferably Ci-C 4 alkyl, C 6 -C 25 -alkylcarboxyl, more preferably C 8 -C 2 o-Alkylcarboxyl, in particular for hydrogen, C ⁇ -alkylcarboxyl or Ci 5 -alkylcarboxyl or for the rest
- ortho-phosphoric acid pyrophosphoric acid, polyphosphoric acids, benzenephosphonic acid, benzoic acid, benzenesulphonic acid, toluenesulphonic acid, dodecylbenzenesulphonic acid and all other phenyl-substituted benzenesulphonic acids and esters, monoesters and bridged esters of the abovementioned acids, such as, for example, toluenesulphonic acid esters, phosphoric esters, phosphorous acid phosphonic esters and others acid-forming components such as tri-iso-octyl phosphate, Ultranox® 640 and BDP in question.
- the metered addition of the acidic components can take place in solid, liquid or gaseous form.
- the acidic component is continuously mixed homogeneously into the product stream to be liberated from the monomers in the production process directly after reaching the desired final molecular weight in order to immediately start evaporation of the residual monomers.
- the additive is carried out to improve individual product properties behind the acid dosage and the residual monomer reduction and not combined with the step of residual monomer reduction, because often additives are used, which in the vacuum, which is essential for the reduction of the residual monomers, volatile are and then poorly adjust in the required concentrations in the polymer.
- the acidic components are added in liquid form. Since the amounts to be metered are very low, solutions of the acidic components are preferably used.
- Suitable solvents are those which do not interfere with the process, are chemically inert and evaporate rapidly.
- Suitable solvents are all organic solvents having a boiling point at normal pressure of 30 to 300 0 C, preferably from 30 to 250 0 C and more preferably from 30 to 200 0 C and water - including Kristaiiwasser - in question.
- those compounds are selected which occur in the respective processes. Depending on the requirement profile of the product to be produced, any remaining residues do not reduce the quality.
- solvents include alkanes, cycloalkanes and aromatics, which may also be substituted.
- the substituents may be aliphatic, cycloaliphatic or aromatic radicals in various combinations as well as halogens or a hydroxyl group. Heteroatoms, such as oxygen, may also be bridge members between aliphatic, cycloaliphatic or aromatic radicals, where the radicals may be the same or different.
- Further solvents may also be ketones and esters of organic acids and cyclic carbonates.
- Examples are, in addition to water, n-pentane, n-hexane, n-heptane and their isomers, cyclohexane, toluene and xylene, methylene chloride, ethyl chloride, ethylene chloride, chlorobenzene, methanol, ethanol, propanol, butanol and their isomers, phenol, , m- and p-cresol, diethyl ether, dimethyl ketone, polyethylene glycols, polypropylene glycols, ethyl acetate, ethylene carbonate and propylene carbonate.
- suitable for the polycarbonate process are water, phenol, propylene carbonate, ethylene carbonate and toluene.
- Particularly suitable are water, phenol and propylene carbonate.
- static mixers or other mixers leading to homogeneous mixing are suitable.
- the polycarbonates according to the invention can be subjected to residual degassing of monomers (eg diphenyl carbonate, phenol, BPA) and short oligomers and small rings after prior or simultaneous deactivation (quenching) of catalyst residues.
- monomers eg diphenyl carbonate, phenol, BPA
- short oligomers and small rings after prior or simultaneous deactivation (quenching) of catalyst residues.
- This can be with or without towing gas, e.g. Nitrogen, in the last reactor or a downstream degassing aggregate can be achieved.
- the present application also relates to extrudates and shaped articles, in particular those for use in the transparent region, which are obtainable from the compositions according to the invention.
- Areas of application may be: safety disks, shields of helmets, foils, blown bodies such as water bottles, translucent panels, such as solid panels or in particular hollow panels, for example for covering buildings such as stations, greenhouses and lighting systems, traffic light housing or traffic signs, foams with open or closed optionally printable Surface, threads and wires (sa DE-A 11 37 167), lighting applications, optionally using glass fibers for applications in the translucent area, translucent settings containing barium sulfate and or titanium dioxide and or zirconium oxide or organic polymeric acrylate rubber ken (EP-A 0 634 445, EP-A 0 269 324) for the production of translucent and light-scattering molded parts, precision injection-molded parts, such as holders, eg lens holders;
- polycarbonates with glass fibers and an optionally additional content of 1-10% by weight of molybdenum disulfide (based on the entire molding composition) are used, optical device parts, in particular lenses for photo and film cameras (DE-A 27 01 17
- the relative solution viscosity ⁇ re i also referred to as eta rel was determined in dichloromethane at a concentration of 5 g / l at 25 ° C with a Ubbelohdeviskosimeter.
- the content of phenolic OH was obtained by IR measurement.
- a difference measurement of a solution of 2 g of polymer in 50 ml of dichloromethane was measured against pure dichloromethane and the difference in extinction at 3582 cm ' * determined.
- the flow behavior (melt viscosity) of the polymer melts is determined at different temperatures in a capillary rheometer according to ISO 11443.
- the polycarbonate samples are previously dried for this purpose at 130 0 C overnight.
- the shear rates are given in s "1 .
- the sample is dissolved with methylene chloride. By adding acetone, the majority of the polymer is precipitated. The undissolved portions are filtered off, the filtrate is concentrated to dryness. The dry residue is dissolved with THF and the oligomers are determined by HPLC with UV detection.
- the polycarbonate sample is saponified with sodium methylate under reflux.
- the saponification solution is acidified and concentrated to dryness.
- the dry residue is dissolved with acetonitrile and the phenolic compounds (Ia to IVa) are determined by HPLC with UV detection.
- the polycarbonate composition PC1 was prepared in a melt process as follows.
- the melt is then passed through an expansion valve in a below 200 mbar separator.
- the melt flowing is heated in a, likewise under 200 mbar, FAIL i ⁇ lmverdampfer again to 190 0 C and collected in a receiver.
- the melt is pumped into the next three, similarly constructed stages.
- the conditions in the 2nd / 3rd / 4th stages are 100/74/40 mbar; 220 0 C / 225 ° C / 273 ° C and 20/10/10 minutes.
- the resulting oligomer has a rel. Viscosity of 1.08. All breeder
- the pressure regulators are passed into a column under vacuum and discharged as condensates.
- the oligomer is condensed in a subsequent disk reactor at 290 0 C and 0.7 mbar at a residence time of 120 minutes to a higher molecular weight product.
- the rel. Viscosity is 1.257.
- the vapors are condensed.
- the vapors are condensed in the vacuum system and behind it.
- polycarbonate compositions PC3, PC5 and PC7 are prepared analogously to PCl, the BPA being adjusted to DPC ratio such that the higher vicosities are obtained eta rel.
- PC2, PC4, PC6 and PC8 are comparative examples in which the polycarbonate compositions were recovered by the interfacial method.
- Table 1 shows the data of the polycarbonate compositions prepared according to the above experiments, including the determined rearrangement structure and oligomer contents and the nonuniformity U:
- the polycarbonates of the invention PCl, PC3, PC5 and PC7 have significantly lower levels of cycles than the corresponding comparative examples PC2, PC4, PC6 and PC8. Nevertheless, in each case a better flow behavior of the polycarbonates according to the invention is rounded. Surprisingly, it has been found that the process always yields a nearly constant and lower amount of cycles, whereas, on the other hand, the comparative examples have higher proportions of cycles with increasing viscosity.
- polycarbonates according to the invention have a significantly narrower MW distribution (smaller nonuniformity U) despite the presence of polyfunctional rearrangement structures (branchings).
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
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Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES09733376T ES2394418T3 (en) | 2008-04-18 | 2009-04-09 | Polycarbonates with transposition structures, cyclic and linear oligomers as well as improved flow behavior |
CN2009801136222A CN102007161B (en) | 2008-04-18 | 2009-04-09 | Polycarbonates with rearrangement structure, cyclic and linear oligomers and improved flow behavior |
RU2010146694/04A RU2496801C9 (en) | 2008-04-18 | 2009-04-09 | Improved fluidity polycarbonates containing regrouped structures, cyclic and linear oligomers |
EP09733376A EP2268706B1 (en) | 2008-04-18 | 2009-04-09 | Polycarbonates having rearrangement structures, cyclic and linear oligomers and also improved flow behaviour |
JP2011504358A JP5620367B2 (en) | 2008-04-18 | 2009-04-09 | Polycarbonate with improved flowability with dislocation structure, cyclic and linear oligomers |
KR1020107023078A KR101669684B1 (en) | 2008-04-18 | 2009-04-09 | Polycarbonates having rearrangement structures, cyclic and linear oligomers and also improved flow behaviour |
PL09733376T PL2268706T3 (en) | 2008-04-18 | 2009-04-09 | Polycarbonates having rearrangement structures, cyclic and linear oligomers and also improved flow behaviour |
US12/988,456 US8158745B2 (en) | 2008-04-18 | 2009-04-09 | Polycarbonates having rearrangement structures, cyclic and linear oligomers and also flow behavior |
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DE102008019503A DE102008019503A1 (en) | 2008-04-18 | 2008-04-18 | Polycarbonates with rearrangement structures, cyclic and linear oligomers and improved flow behavior |
DE102008019503.0 | 2008-04-18 |
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PCT/EP2009/002662 WO2009127366A1 (en) | 2008-04-18 | 2009-04-09 | Polycarbonates having rearrangement structures, cyclic and linear oligomers and also improved flow behaviour |
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US (1) | US8158745B2 (en) |
EP (1) | EP2268706B1 (en) |
JP (1) | JP5620367B2 (en) |
KR (1) | KR101669684B1 (en) |
CN (1) | CN102007161B (en) |
DE (1) | DE102008019503A1 (en) |
ES (1) | ES2394418T3 (en) |
PL (1) | PL2268706T3 (en) |
RU (1) | RU2496801C9 (en) |
TW (1) | TWI481641B (en) |
WO (1) | WO2009127366A1 (en) |
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WO2019238419A1 (en) | 2018-06-14 | 2019-12-19 | Covestro Deutschland Ag | Transesterification method for simultaneously producing at least two different polycarbonates in a production facility |
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PL2268706T3 (en) | 2013-02-28 |
JP5620367B2 (en) | 2014-11-05 |
US8158745B2 (en) | 2012-04-17 |
TWI481641B (en) | 2015-04-21 |
JP2011516700A (en) | 2011-05-26 |
US20110040066A1 (en) | 2011-02-17 |
ES2394418T3 (en) | 2013-01-31 |
RU2496801C9 (en) | 2014-07-10 |
DE102008019503A1 (en) | 2009-10-22 |
RU2496801C2 (en) | 2013-10-27 |
EP2268706A1 (en) | 2011-01-05 |
EP2268706B1 (en) | 2012-10-03 |
TW201004999A (en) | 2010-02-01 |
CN102007161A (en) | 2011-04-06 |
RU2010146694A (en) | 2012-05-27 |
KR20100133436A (en) | 2010-12-21 |
CN102007161B (en) | 2013-02-06 |
KR101669684B1 (en) | 2016-10-27 |
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